JP2849134B2 - Improved titania catalyst, its preparation and use in Fischer-Tropsch synthesis - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Field of the Invention The present invention relates to a Fischer-Tropsch process and an improvement of a Fischer-Tropsch catalyst. For more cobalt catalyst present invention was improved, a manufacturing method of the catalyst, as well as liquid hydrocarbons, to the use of the catalyst in Fischer-Tropsch synthesis especially production of C ₁₀ + distillate fuels and other useful products .

(2) Background of the Invention Fischer-Tropsch synthesis, the production of hydrocarbons from carbon monoxide and hydrogen, ie, synthesis gas, is well documented in the technical and patent literature. The Fischer-Tropsch process is also used commercially and is in operation today in some parts of the world.

These and other recently developed forms of cobalt-titania catalysts can be prepared by dispersing such catalysts, particularly one of Co-Re, Co-Hf and Co-Ce, and other forms of rutile titania. Shows the feasibility of a viable modern large-scale commercial Fischer-Tropsch plant that can utilize the catalyst formed by E.I. However, despite the exceptionally high activity and selectivity of these catalysts, there remains a need for further improvements in the activity, selectivity and productivity of Fischer-Tropsch catalysts, and especially cobalt catalysts. The productivity, defined as standard volume of converted carbon monoxide / catalyst volume / hour, is of course the vitality of commercial operation. High productivity is essential for achieving commercially viable operation. However, it is also essential that high productivity is achieved without high methane formation,
This is because methane production results in low production of liquid hydrocarbons.

(3) Purpose Accordingly, a main object of the present invention is to provide a novel and improved titania carrier and a supported catalyst composition.

In particular, the object of the present invention is to provide a titania carrier and a titania-supported catalyst composition, a process for preparing said catalyst composition and a syngas with high productivity, low methane formation and high quality fraction fuels, in particular C ₁₀ + linear paraffins. And a method for utilizing the catalyst composition for conversion to olefins.

It is a particular object of the present invention to provide an improved porosity titania support and a titania supported cobalt catalyst composition that produces a minimal pressure drop across the reactor when used in a hydrocarbon synthesis reaction dispersed in a reactor bed; An object of the present invention is to provide a catalyst having the above properties and having physical strength.

Another object is to provide a method of utilizing the catalyst composition, to produce a C ₁₀ + linear Parain and olefins with a low methane selectivity at high productivity from a gas mixture.

It is also an object to provide a process for preparing the above supports and catalysts.

(4) Invention These and other objects are to provide a novel binder-containing titania carrier, a particulate catalyst formed by dispersing a catalytically effective amount of a metal catalytically active in carrying out a Fischer-Tropsch reaction on the carrier. And the use of the catalyst in a Fischer-Tropsch reaction. The catalytically active metal, preferably cobalt, is a metal oxide binder selected from the group consisting of alumina, zirconia and silica in a preferred order from about 0.1 to about 20 percent, preferably from about 0.5 to about 20 percent, based on the weight of the total support.
At a concentration in the range of about 10 percent, more preferably about 1 to about 5 percent, the particulate titania, especially at least about 3:
Dispersed on titania with a rutile: anatase ratio of 2. The mixing of these small amounts of binder into titania
Significantly better dispersion and higher dispersion of catalytically active metals, especially cobalt, on the support surface than similar catalysts, except that at low concentrations, no metal oxide binder is present in the titania support component of the catalyst. Produces activity, good selectivity and high productivity. The metal can be distributed substantially uniformly throughout the titania-binder support component of the catalyst outward from the center of the particles, or preferably as a thin catalytically active total or film on the outer peripheral surface of the titania-binder support. These catalysts are capable of converting distillate fuels consisting mainly of linear paraffins and olefins, in particular C ₁₀ + fractions, with low methane selectivity at high productivity by contact and reaction under reaction conditions with a mixture of carbon monoxide and hydrogen. Can be used for manufacturing. The organism higher quality fuels and other products for example motor gasoline, diesel fuel and jet fuel, and in particular purified premium middle distillate fuels of carbon numbers in the range of C ₁₀ ~ about C _20, to luxury goods of be able to.

The titania-binder carrier particles are formed by mixing, blending or otherwise adding the required amount of alumina, zirconia or silica binder to the titania. The presence of the inorganic binder in the indicated amounts, especially at low concentrations, increases the porosity of the titania without eliminating the beneficial effect of the titania in carrying out the Fischer-Tropsch reaction. After the metal is dispersed on the titania-binder carrier, the
In the Tropsch reaction, the behavior as titania substantially continues, but this time the Fischer-Tropsch reaction takes place in a more porous support, so that the activity and selectivity, in particular the productivity, is reduced by the titania base as a binder. , Except that it does not contain, the same is the case. An even greater advantage is that, based on the total amount of titania-binder carrier particles,
It will be appreciated that it can be obtained by using a binder in an amount not exceeding 10 percent, preferably not exceeding about 5 percent. Binders can be used at concentrations greater than about 10 percent, and as high as about 20 percent, but use of the binder at these higher concentrations generally does not provide any benefit; There can be.

Catalysts formed by dispersing metals, in particular cobalt, or cobalt and other metals or metals as cocatalysts or modifiers, such as rhenium, hafnium, cerium, on a titania-binder carrier have sufficient binder components. The presence of lower concentrations continues to provide not only the usual benefits of the titania carrier component, but also more, ie, higher activity and selectivity, and higher productivity at low methane production. The titania-binder carrier component continues to behave like titania, but high porosity titania, if the binder component is present at a sufficiently low concentration. Furthermore, despite the high porosity and its advantages, the catalyst has good physical strength. Typically pore volume (Hg) less than 0.2 cc / g
The porosity of the titania having the above is increased to 0.2 cc / g or more, preferably from about 0.2 to about 0.5 cc / g, more preferably from about 0.25 to about 0.35 cc / g, About 70m ² /
g, preferably in the range of about 10 to about 30 m ² / g. It is believed that these advantages are obtained and that a significantly better dispersion of the metal or metals is achieved on the high porosity support, which results in high hydrocarbon synthesis activity, selectivity and productivity.

Titania-alumina supports are preferred. "Fumed" titania and aluminum consisting of very small micron-sized particles produced by the oxidation of titanium tetrachloride
Alumina binder prepared by the hydrolysis of sec-butoxide is a preferred material for the production of titania-alumina carrier particles. In the production of titania-alumina carrier particles, the preferred method of producing these particles involves mixing titania with the desired proportions of alumina binder, water, and preferably a lubricant, suitably methylcellulose or polyglycol, and then extruding. Molding. It has been found that titania crystallite size and particle size are particularly important for achieving satisfactory extrusion suitability. (Uristalit refers to the smallest individual particles of titania consisting of an ordered array of titanium and oxygen atoms.) The size of titania crystallites used in the extrusion mixture is a measure of the line width of the main anatase or rutile peak in the X-ray analysis diagram. An average crystallite size of no more than about 1000 angstroms, preferably an average crystallite size in the range of about 200 to about 600 angstroms, and an average particle size of titania, e.g.
If appropriate, use a Microtrac Analyzer
It is especially preferred for good extrudability that it is no greater than about 10 microns, preferably about 0.5 to 5 microns as measured by an Analyzer). The extrusion itself is carried out in a conventional manner with low torque, producing a "green" extrudate of virtually any desired cross section. Suitably, for example, the extrudate is 1 /
20 inch diameter trilobate, also 1/32
It is in the form of an inch diameter cylinder. In performing the extrusion,
If the average crystallite size of the titania is too large or the average particle size is too large, the titania-alumina mixture is difficult to extrude and the extrudate lacks the proper strength required for a catalyst support. (In contrast, alumina with an average particle size of 5 to 75 microns can be easily extruded in the absence of titania without significant variation in its extrusion properties.) The extruder mold or extrudate morphology Virtually any type of extruder can be used to form the extrudate, as it does not significantly affect the porosity or surface area of the shaped titania-binder carrier. Green extrudates are typically from about 90 to about 15
Drying by heating at a temperature in the range of 0 ° C., preferably in the range of about 110 to about 120 ° C .;
By heating to the above temperature, preferably about 500 ~
It can be calcined by heating to a temperature in the range of about 850 ° C. Since the anatase is converted to rutile,
It is desirable to minimize the calcination temperature and time to conditions where the surface area is reduced during calcination, thus providing exactly the desired rutile content.

The catalytically active metal or metals, preferably cobalt or cobalt promoted or modified with additional metals or metals, may be distributed in a manner that uniformly distributes the metal or metals from the center outwards throughout the particle. It can be dispersed on the calcined titania-binder carrier particles or substantially on the surrounding surface of the particles, the latter being preferred.
For example, the catalyst can be prepared from calcined titania-binder carrier particles by methods known in the art for the preparation of other catalysts. In order to distribute the metal or metals evenly throughout the calcined titania-binder carrier particles, for example, the metals or metals are pre-coated to give the desired absolute amounts and weight ratios of the respective metals or metals on the carrier particles. A selected amount can be precipitated from the solution. Suitably, for example, cobalt, or cobalt and rhenium, is complexed with the carrier by contacting the carrier with a solution of a cobalt-containing compound or salt or a rhenium-containing compound or salt, followed by impregnation with other components. Optionally, cobalt or cobalt and rhenium can be co-impregnated on the support. The cobalt used for the impregnation can be any organometallic or inorganic compound which decomposes upon calcination to give a cobalt oxide, such as cobalt nitrate, acetate, acetylacetonate, naphthenate, carbonyl and the like. Similarly, the rhenium compound used for the impregnation can be any organometallic or inorganic compound that decomposes upon calcination to give a rhenium oxide, such as perrhenic acid, ammonium perrhenate and the like. The amount of impregnating solution used should be in the range of about 1 to 20 times the volume of the support, sufficient for the complete immersion of the support, usually depending on the metal or metals, concentration in the impregnating solution. The impregnation can be performed under a wide range of conditions including room temperature or high temperature. On the other hand, the catalytically active cobalt component is most preferably present on the surrounding surface of the calcined titania-binder particles at about 20 to about
About 0.01 to about 0.15 grams (g) per cubic centimeter (cc), preferably about 0.03 to about 0.09, as a thin catalytically active surface layer or film within an average thickness of 250 microns, preferably about 40 to about 150 microns. Dispersed and loaded with a cobalt load, expressed as the catalyst bulk volume per weight of metal cobalt within the g / cc catalyst range. The feature of high cobalt metal loading in a thin catalytically active layer located on the surface of the particles is to optimize the activity, selectivity and productivity of the catalyst in the production of liquid hydrocarbons from synthesis gas while minimizing methane formation Can be.

The surface impregnated catalyst can be prepared by a spray technique in which a dilute solution of the cobalt compound alone or in a mixture with the co-catalyst metal compound or compounds is repeatedly contacted with the hot titania-binder carrier particles as a spray. The particulate carrier particles are maintained at a temperature equal to or greater than about 140 ° C. when contacted with the spray, and suitably the temperature of the titania-binder carrier particles is from about 140 ° C. to the compound in the cobalt compound or mixture therewith. Up to the decomposition temperature of
Preferably it is in the range of about 140 to about 190C. The cobalt compound used in the solution is any organometallic or inorganic compound that decomposes on initial contact or calcination to give a cobalt oxide, such as cobalt nitrate, cobalt acetate, cobalt acetylacetonate, cobalt naphthenate, cobalt carbonyl Can be Cobalt nitrate is particularly preferred and cobalt halides and sulphates are generally to be avoided. The cobalt salt is a suitable solvent, such as water,
Organic or hydrocarbon solvents such as acetone, methanol,
It can be dissolved in pentane and the like. The total volume of solution used should provide adequate catalytic loading and should be sufficient for the film to be established by repeated contact between the carrier and the solvent. Preferred catalysts are titania-binder carrier,
In particular, the titania moiety consists essentially of cobalt dispersed on a support consisting of rutile, or of cobalt and a cocatalyst. Suitably, the thermal titania-bound carrier particles comprise a cobalt compound or a cobalt compound plus a promoter metal compound, from about 0.05 to about 0.25 g / ml, preferably from about 0.10 to about 0.
A spray containing 20 g / ml is generally contacted with at least about 3 to about 12 contacts, preferably about 5 to about 8 contacts, and an intervening drying and calcining step is required to form a surface film of the required thickness. In other words, to form a film of the required thickness and composition, the hot titania-binder carrier particles are subjected to a first cycle comprising spray contact itself and subsequent drying and calcination, itself and subsequent drying and calcination. Spray contact, such as during a second cycle involving calcination. The drying stage is generally about 20 ° C
Above, preferably at a temperature in the range of about 20 to about 125C, the calcination step is performed at a temperature of about 150C or more, preferably in the range of about 150 to about 300C.

Metals such as rhenium, zirconium, hafnium, cerium, thorium and uranium, or compounds thereof, can be added to cobalt to enhance the activity and regenerability of the catalyst. Therefore, catalysts containing cobalt metal uniformly dispersed throughout the carrier particles, or those in which cobalt is dispersed as a thin catalytically active layer or film on the carrier particles, include rhenium, zirconium, hafnium, cerium in addition to the catalytically active amount of cobalt. , Uranium and thorium, any one or more of them, their fittings, or mixtures of these with other metals or compounds thereof. Thus, preferred catalytically active metals are cobalt-rhenium, cobalt-zirconium, cobalt-
Hafnium, cobalt-cerium, cobalt-uranium and cobalt-thorium are included in the presence or absence of other metals or compounds thereof.

A particularly preferred catalyst is cobalt or cobalt and a cocatalyst dispersed on titania-binder carrier particles, the titania component of which is ASTM D 3720-78: Anatase to rutile in titanium dioxide pigment by use of X-ray diffraction. It has a rutile: anatase weight ratio of at least about 3: 2 as measured by standard test methods for ratios. Generally, the catalyst is one whose titania component has a rutile: anatase ratio in the range of at least about 3: 2 to about 100: 1 or more, more preferably about 4: 1 to about 100: 1 or more. . Rhenium, zirconium, hafnium, cerium,
When any one of the thorium or uranium metals is added to cobalt as a co-catalyst, respectively, the metals can be from about 30: 1 to about 30: 1.
Cobalt is added to a concentration sufficient to provide a weight ratio of cobalt: metal promoter of about 2: 1, preferably in the range of about 20: 1 to about 5: 1. Rhenium and hafnium are the preferred promoter metals, rhenium is more effective in promoting improved activity retention on an absolute basis, and hafnium is more effective on a cost effective basis. These catalyst compositions have low methane selectivity but high productivity, mainly C ₁₀
+ It was found to be a product of linear paraffins and olefins with very little oxygenates.
These catalysts also provide high activity, high selectivity and high activity retention in the conversion of carbon monoxide and hydrogen to distillate fuel.

In the practice of the synthesis gas reaction, the total pressure about CO and H ₂ reaction mixture is generally from about 5.6 kg / cm ² gauge pressure (about 80psi
g) or more, preferably about 9.8 kg / cm ² gauge pressure (about 140 psi).
g) is maintained above. About 0.5: 1 or more of carbon monoxide and hydrogen to increase the concentration of C ₁₀ + hydrocarbons in the product,
It is desirable to use a H ₂ : CO molar ratio preferably equal to or greater than about 1.7: 1. Suitably, H _2: CO molar ratio of about 0.5: 1 to about 4: 1; preferably carbon monoxide and hydrogen is from about 1.7: 1 to about 2.5 molar ratio in the 1 range
H ₂ : Used in CO. Generally, the reaction is carried out at about 100 to about 5000 V / hr / V, preferably about 300 to about 1500 V / hr / V, measured as a standard volume of gaseous mixture of carbon monoxide and hydrogen (0 ° C., 1 atmosphere) per hour per catalyst volume. It is performed at a gas hourly space velocity in the range of V. The reaction is performed at a temperature in the range of about 160 to about 290C, preferably about 190 to about 260C. The pressure is preferably about 5.6 to about 42.2 kg / cm ² gauge pressure (about 80 to about 600 ps
ig), more preferably about 9.8 to 28.1 kg / cm ² gauge pressure (about 1
40 to about 400 psig). The product is generally preferably 60 percent or more, more preferably
Of 75 percent or more, including C ₁₀ + liquid hydrocarbons boiling at 160 ° C. (320 ° F) or higher.

In the first set of tests below, titania and alumina,
The silica and zirconia are each mixed to form titania-binder carrier particles, wherein the binder is in the concentration range of 1 to 21 percent and more based on the weight of the carrier particles, and the titania is titania- A series of preparations that make up the balance of the binder carrier particles are described. The pore volume and surface area of different titania-binder compositions of different shapes are compared to binder-free titania carrier particles.

Example 1 In a first series of preparations, titania was mixed with an alumina, silica or zirconia binder. The alumina binder is produced by hydrolysis of Al (OC ₄ H ₉ ) ₃ or the titania-alumina composite is made of Al (OC ₄ H ₉ ) ₃ and Ti (OC ₃ H ₃ ) _3.
Was prepared by co-hydrolysis of H _{7) 4.} Titania was purchased directly from commercial sources. The titania was mixed well with the alumina binder, water and lubricant-methosel or polyglycol. The mixture is low in torque when extrudates are formed.
8 inch Welding Enginee
r) Extrusion equipment or Carver Pres
s) Trilobes (T
RIL) or extruded as 1/32 inch diameter cylinders (1/32), dried at 120 ° C and then calcined at 500-850 ° C.

The individual preparations are indicated by reference to Table 1 and have the carrier nos.
8 (and 47) indicate pure titania in both extrudate and sphere form prepared without binder as a standard.
Carrier Nos. 9-14 (and 43-46) in Table 1 are extrudates containing more binder than titania except for three cases, including some examples of pure alumina extrudates. Carriers Nos. 15-41 exemplify the carriers of the present invention, and these carriers show the effect of binder content at various concentrations. Carriers Nos. 15 to 22 show in particular the effect of alumina binder content using the trilobate form calcined at 650 ° C. The higher the added alumina, the higher the resulting pore volume and surface area. Carrier No.23~29 Preferred compositions shown, i.e. _{96.5% TiO 2 /3.5%Al 2 O 3} , the effect of calcination related. Carriers Nos. 30-33 show that steaming is equivalent to calcination and both convert anatase to rutile, resulting in a decrease in surface area. Pore volume also decreases and median pore diameter increases. A wide range of alumina-containing materials have been demonstrated to be useful as binders. Pure alumina gels and titania-alumina cogels prepared by alkoxide hydrolysis are as satisfactory as many different commercial aluminas. Carriers Nos. 37-41 show that silica and zirconia also function as binders, and that other sources of titania are suitable starting materials.

Next, "Legend of Table Heading" and Table 1 will be described. The legend gives background information for Table 1.

These data are based on pore volume (PV) measured by mercury porosimetry in FIG. 1 versus surface area (SA) by BET analysis.
Is illustrated by a plot of The data points fall into two different categories: (1) a lower curve for a pure titania carrier or a titania carrier without a binder, and (2) an upper curve for a titania carrier with a binder. As indicated by the use of different symbols, the upper curve can be broken down into substances containing more than about 20 percent (closed squares) or less than (closed circles) binder. The latter show a significantly higher pore volume than pure titania or titania without binder at a given surface area. The exact level of pore volume and surface area within the lower part of this curve is obtained by varying the binder content between about 1-20% and varying the final calcination temperature appropriate for the support. Increasing binder concentration increases pore volume and surface area. Increasing the calcination temperature reduces the pore volume and surface area. Optimally, the amount of binder used should not exceed about 10 percent, and preferably should not exceed about 5 percent.

Extrudate shaped catalysts offer advantages over other forms to the process, and as suggested earlier, titania crystallite size and particle size are carefully controlled for satisfactory extrusion and to obtain satisfactory extrudate Should. The following examples illustrate the importance of titania crystallite size and particle size.

Example 2 The following Table 2 lists the results of a series of extrusion tests with various titanias from various sources. The table shows the anatase and rutile composition, crystallite size in Angstroms, average particle size diameter of titania in microns, and
3 in 0.8 inch welding engineer extruder
Gives the extrudable properties of titania in the production of 1/32 inch diameter extrudates by passing the titania through a hole die.

It is clear that good performance is obtained only when the crystallite size is less than about 1000 Angstroms, preferably less than about 600 Angstroms, and the particle size is less than about 5 microns, preferably less than about 2 microns. If either property exceeds these values, titania is difficult to extrude. Often, when such conditions are not met, the extruder becomes clogged and the resulting extrudate is very weak.

Example 3 This example illustrates the use of a high porosity titania-binder support as a catalyst for a Fischer-Tropsch synthesis, i.e., the production of hydrocarbons from carbon monoxide and hydrogen. The data show that significantly better metal dispersion and higher hydrocarbon synthesis activity occur when cobalt is dispersed on a more porous support.

Table 3 lists the catalysts prepared from the supports indicated in Table 1 and each support is identified in Table 3 by a number corresponding to that shown in Table 1. Table 3 The composition of the catalyst prepared from the support, giving at their O ₂ chemisorption and performance in hydrocarbon synthesis test. The catalyst was prepared by impregnating the support on a rotary evaporator with an acetone solution of cobalt nitrate and perrhenic acid, drying in a vacuum oven at 140 ° C. and calcining in an oven at 250 ° C. in flowing air. Oxidation chemisorption was performed at 25 ° C by measuring the absorption of oxygen pulses from a helium carrier gas stream passed over a sample of the catalyst reduced at 450 ° C in hydrogen for 16 hours.
The catalyst test was performed in the apparatus with a small charge of catalyst diluted with an equal volume of titania. The catalyst was ground, sieved to 60-150 Tyler mesh size, and reduced in hydrogen at 450 ° C. for 1 hour. The test conditions were 200 ° C., 19.7 kg / cm ² gauge (280 psig) with a feed of 64% H ₂ /32% CO / 4% Ne. The space velocities used for each example are shown in Table 3.

It is useful to indicate the catalyst data by "volume productivity", which is calculated by multiplying the converted fraction CO x space velocity x fraction CO in the field. High volume productivity is a highly desirable property of the catalyst because reactor volume is an expensive item. For hydrocarbon synthesis on a cobalt catalyst,
Without diffusion limits, productivity is a factor of three: cobalt loading,
It is a linear function of cobalt dispersion and cobalt oxidation state. It is desirable to maximize loading and dispersion while at the same time keeping the cobalt at zero valence, the only phase active in hydrocarbon synthesis. However, these factors often work counter to each other, so the best catalyst means a compromise. These three factors are considered in the definition of the present invention.

The tests performed on these catalysts are summarized in FIG. 2, which plots "cobalt productivity" versus binder content in the support. Cobalt productivity is calculated by simply dividing volumetric productivity by the volumetric cobalt load. As shown in FIG. 2, the cobalt productivity increases significantly with the addition of a small amount of binder and then drops after more than 20% of binder. This activation credit is the key and novel feature of the present invention.

Increased activity due to incorporation of small amounts of binder results in increased cobalt dispersion. O ₂ chemisorption analysis shows that the O / Co ratio, a measure of relative variance, correlates with the pore volume of the support. Thus, since the binder increases the pore volume of the carrier,
Dispersion increases for the catalyst. This trend actually continues all the way to pure alumina. However, the hydrocarbon synthesis activity does not continue to increase as the binder is added. In fact, the activity is reduced because the support becomes too "alumina-like". X
Surface analysis by line photoelectron spectroscopy shows that cobalt oxide is only partially reduced on alumina as compared to titania, which produces complete reduction. Thus, too much binder gives high dispersion but this potential advantage is more than offset by poor reducibility.

The difference between titania and alumina is very clearly shown by converting the cobalt productivity values into "turnover numbers" as follows: The plot of TON vs. binder content, FIG. 3, shows a sharp decrease in "intrinsic" activity with incorporation of binder into the carrier. Less than 20%, preferably less than 10%, and most preferably less than 5% of the binder should be present to maintain the highest cobalt turnover number.

Thus, the volumetric productivity of the catalyst can be increased when the appropriate amount of binder is not diffusion limited. This is an important result for all catalyst forms, especially including those in powder form. However, more porous support credits become more important when some diffusion limitations are encountered, as is the case with many fixed-bed catalysts. In this regard, excess porosity helps reactant diffusion, resulting in additional activity and significant selectivity advantages. This feature of the present invention is described, for example, by Froment and Bischoff in "Chemical Reactor Analysis and Design".
CIOR ANALYSIS AND DESIGN) on page 167.

Example 4 Tests 48 and 49, summarized in Table 4, are catalysts with cobalt coated on the surface of the support and these data show the advantage of improved porosity under some diffusion-limited conditions . The catalyst was prepared by repeated spraying of the heat carrier particles with an aqueous solution of cobalt nitrate and perrhenic acid. The volumetric cobalt load and the thickness of the surface metal coating are substantially constant in this comparison. Thus, the productivity and selectivity credit of test 49 as compared to test 48 can be reduced to the use of a more porous support containing 3.5% alumina as a binder.

Thus, these data clearly show that titania supports with improved porosity provide superior properties when used in the manufacture of cobalt hydrocarbon synthesis catalysts.
High porosity results in good cobalt dispersion, which results in high intrinsic hydrocarbon synthesis activity. High porosity is also beneficial in the form of catalysts that are somewhat diffusion limited, eg, surface metallized.

Hydrocarbon synthesis reactions can be considered with or without recycle of unconverted gas and / or liquid products in fixed bed or boiling bed reactors with these catalysts.
The resulting C ₁₀ + product is a mixture of linear paraffins and olefins, which can be further refined and upgraded to high quality middle distillate fuels or automotive gasoline, diesel fuel, jet fuel, and the like. About C ₁₀ to about C
Premium grade middle distillate fuels with carbon numbers in the range of ₂₀
It can be prepared from C ₁₀ + hydrocarbon product.

Obviously, various modifications or changes can be made without departing from the spirit and scope of the invention.

[Brief description of the drawings]

FIG. 1 shows a plot of pore volume (PV) measured by mercury porosimetry versus surface area (SA) by BET analysis, and FIG. 2 shows the cobalt productivity versus binding in the support of a test performed with the catalyst of the present invention. FIG. 3 shows a plot of agent content, and FIG. 3 shows a plot of turnover number versus binder content in the carrier.

──────────────────────────────────────────────────の Continuation of front page (51) Int.Cl. ⁶ Identification code FI C07C 11/02 C07C 11/02 // B01J 21/06 B01J 21/06 Z C07B 61/00 300 C07B 61/00 300 (56) References JP-A-62-65749 (JP, A) JP-A-59-102440 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) B01J 21/00-38/74

Claims (8)

(57) [Claims] An inorganic oxide binder selected from the group consisting of alumina, zirconia and silica, dispersed on a titania carrier that is 0.1 to 20 percent mixed based on the weight of the titania binder carrier. A catalyst composition comprising a catalytically effective amount of cobalt active for the conversion of gas to hydrocarbon. 2. The titania binder carrier having a pore volume of 0.2 to 0.2.
0.5 cc / g have a in the range of surface area is within the range of 8~70m ² / g, according to claim (1) composition. 3. The composition of claim 2, wherein the cobalt is promoted with a metal selected from the group consisting of rhenium, hafnium, zirconium, cerium, thorium, and uranium. 4. The composition according to claim 1, wherein the titania component of the carrier has a rutile: anatase weight ratio of at least 3: 2. 5. The titania component of the carrier having a rutile: anatase weight ratio in the range of 3: 2 to 100: 1 and higher.
The composition according to claim (4). 6. An inorganic oxide binder having a titania content of 0.5%
The composition of claim 1, wherein the composition is included at a concentration in the range of 10 percent. 7. The composition according to claim 1, wherein the catalyst metal is cobalt and the inorganic oxide binder is alumina. 8. A process for converting synthesis gas into hydrocarbons with high activity, comprising the step of reacting a mixture of carbon monoxide and hydrogen at a H ₂ / CO molar ratio equal to or greater than 0.5: 1 under reaction conditions. A method comprising contacting the feed with a catalyst composition according to any one of claims (1) to (7) at a pressure greater than or equal to 5.6 kg / cm ² gauge pressure.